Evaluation of the energy transfer rate for the Yb3+:Pr3+ system in lead fluoroindogallate glasses

E. Pecoraro, D. F. de Sousa, R. Lebullenger, A. C. Hernandes, and L. A. O. Nunes Citation: J. Appl. Phys. 86, 3144 (1999); doi: 10.1063/1.371180 View online: http://dx.doi.org/10.1063/1.371180 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v86/i6 Published by the American Institute of Physics.

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JOURNAL OF APPLIED PHYSICS

VOLUME 86, NUMBER 6

15 SEPTEMBER 1999

Evaluation of the energy transfer rate for the Yb3 :Pr3 system in lead uoroindogallate glasses
E. Pecoraro, D. F. de Sousa, R. Lebullenger, A. C. Hernandes, and L. A. O. Nunes
Instituto de Fsica de Sao Carlos, Universidade de Sao Paulo, Avenida Dr. Carlos Botelho 1465, CEP 13560-970, Sao Carlos SP, BRAZIL

Received 1 March 1999; accepted for publication 2 June 1999 In this article, we report on spectroscopic studies of Pr3 :Yb3 codoped lead uoroindogallate glasses. By pumping with a diode laser in 0.98 m, it was veried that the intensity of infrared luminescence at 1.3 m of Pr3 ( 1 G 4 3 H 5 ) is highly increased approximately 40 times by the presence of Yb3 . Anti-Stokes luminescence upconversion , which represents a loss mechanism for the infrared emission, was also observed. These features were attributed to an efcient energy transfer process from Yb3 to Pr3 . Calculation of the energy transfer constant (C s a ) and energy transfer rate ( P s a ) showed that the process from Yb3 to Pr3 is nearly one order of magnitude greater than in the opposite direction. The energy transfer efciency obtained was about 92%. The best molar ratio Pr3 :Yb3 is 1:4 for both infrared and upconverted luminescence signals. 1999 American Institute of Physics. S0021-8979 99 06517-2

I. INTRODUCTION

Considerable interest has been shown over the last few years for optical devices operating at 1.3 m, such as optical ampliers and lasers.1 These devices have applications in optical communications due to the second telecommunications window in which most ber networks operate. A low phonon energy matrix, such as uoride or chalcogenides, is desired in order to observe the Pr3 transition 1 G 4 3 H 5 which generates 1.3 m photons. This is due to the high multiphonon decay rate from the 1 G 4 level of Pr3 to the 3 F 4 level. Fluorozirconate glasses like ZBLAN have been used as hosts for Pr3 in the search for optical ampliers in this area and practical devices can be demonstrated.1 Codoping with Yb3 is a well-known method to increase the pump efciency at about 0.98 m by means of Yb3 rare-earth energy transfer.2,3 Such a process has been used in Yb3 :Pr3 doped systems.4,5 Also, Tm3 is found in the codoping of uoride6 and phosphate7 glasses with Pr3 . Additionally, Mn2 has been used in phosphate glass8 to increase the infrared emission of Pr3 under ultraviolet excitation. In a previous work,9 Pr3 single doped samples were studied in lead uoroindogallate glasses and it was observed that the best sample to emit at 1.3 m was doped with 1 mol % of Pr3 . It has been argued that in Pr3 the rst excited conguration lies very close to the 4 f 2 conguration, causing a breakdown in standard JuddOfelt JO theory. This fact could lead to negative values for the parameters. According to Florez et al.,10 the JO calculations were made taking into account both odd and even rank tensors in the guring of the phenomenological parameters and in this way we avoided the appearance of negative values for them. It was found that the contribution of the odd terms to the calculated oscillator strength was about 30% and the rootmean-square error rms dened by rms ( ( f meas 2 f calc) 2 / f calc) 1/2 was close to 6%, whereas f meas and f cal
0021-8979/99/86(6)/3144/5/$15.00 3144

are the measured and calculated oscillator strengths, respectively. Florez et al.10 obtained a rms error of nearly 10% for the measured and calculated oscillator strengths of Pr3 in uoroindate glasses. Other approaches have been used to calculate JO parameters in Pr3 doped systems. In a paper by Quimby and Miniscalo,11 the measured branching ratios were included to determine the even JO parameters of Pr3 in ZBLAN glasses. This procedure increases the effective number of measured transitions used in the JO calculation, thus enhancing the reliability of the parameters obtained. Kornienko et al.12 took into account noncentral interactions to calculate the oscillator strength of Pr3 in KPrP4O12. It was observed that such treatment allows one to obtain a better value for the 3 H 4 3 P 2 oscillator strength and ensures that all the JO parameters will be positive. An understanding of the mechanisms involved in the luminescence sensitization of the Yb3 :Pr3 system is a requirement to develop an efcient device operating at 1.3 m pumped by a diode laser at 0.98 m. In this article, we have studied Yb3 Pr3 energy transfer as a mechanism to enhance the infrared emission 1.3 m of Pr3 in lead uoroindogallate glasses. The energy transfer constant (C s a ) and energy transfer rate ( P s a ) were calculated using the ForsterDexter model, showing that the energy transfer from Yb3 to Pr3 is almost one order of magnitude greater than in the opposite direction. Upconverted emissions of Pr3 blue and green were also observed and they represent some loss mechanisms for the infrared emission.
II. EXPERIMENTAL METHODS

The glasses were prepared with the following compositions in mol %: 30 PbF2 20 GaF3 15 InF3 15 ZnF2 (20 x y) CaF2 y YbF3 x PrF3 with x 1 and y 0, 1, 2, 4, and 6 . The starting materials were optical grade PbF2, CaF2, ZnF2, and PrF3 from Fluortran-IR Glass Products Merck and YbF3 3 N , a Strem product. Ga and In were available as
1999 American Institute of Physics

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FIG. 1. Absorption spectra of samples with 1 mol % Pr3 :1 mol % Yb3 and 1 mol % Pr3 obtained at 300 K. The vertical arrows represent the baricenter of each band.

FIG. 2. Infrared luminescence spectra of samples with 1 mol % Pr3 :4 mol % Yb3 and 1 mol % Pr3 obtained at 300 K. The inset shows the variation of the integrated emission band as a function of the Yb3 concentration.

oxides 4 N from PPM Pure Metals GmbH. Aldrichs ammonium biuoride NH4FHF was used to transform each oxide into anhydrous uoride in a dry atmosphere. All these anhydrous uorides were then mixed in a platinum crucible and all the classical steps of melting, rening, and casting were made in a dry glovebox H2O content 10 ppm to prevent hydrolysis. The samples obtained were annealed for several hours at a few below the glass transition temperature, Tg, before cooling them at room temperature. X-ray diffraction showed that all the samples prepared were crystal free. The samples had a thickness of at least 3 mm. Absorption spectra were obtained using a Cary 17 spectrophotometer. For the infrared luminescence and upconversion spectra, the pump source used was a diode laser emitting at 0.98 m. The infrared signal went through a 0.30 m Thermo Jarrel Ash 82497 monochromator and was collected by an EG&G Ge refrigerated coupled photodetector. The upconversion signal was dispersed by a 0.85 m Spex 1403 double monochromator and was collected by an RCA model 31034 coupled photomultiplier. All measurements were done at room temperature.
III. RESULTS A. Absorption

shows the area under the emission band as a function of the Yb3 concentration. For 6 mol % Yb3 , the decrease in the luminescence intensity is attributed to quenching by the Yb3 concentration. From 0 up to 4 mol % Yb3 there is an increase of 40 times in the area under the emission band at 1.3 m. This is attributed to an efcient energy transfer process. The optimum Pr3 concentration 1 mol % was determined previously9 by the observation of the luminescence signal intensity at 1.3 m in a set of Pr3 single doped samples.
C. Upconversion

Figure 3 shows the upconversion spectrum of the sample with 1 mol % Pr3 :4 mol % Yb3 . The inset in Fig. 3 shows the dependence of the upconverted emission at 0.481 m as a function of the Yb3 concentration. All other upconverted emissions follow the same feature with Yb3 concentration. As we have shown in the infrared luminescence results, the

Figure 1 shows the absorption spectra at about 1 m of a single doped 1 mol % Pr3 and a codoped sample (1 mol % Pr3 :1 mol % Yb3 ). The area under the absorption band of the codoped sample Yb3 : 2 F 7/2 2 F 5/2 and Pr3 : 3 H 4 1 G 4 is about 20 times greater than that of the single doped sample and the arrows shown indicate the baricenter of each transition. The 2 F 7/2 2 F 5/2 transition 0.96 m than the (Yb3 ) is in a higher energy position 3 H 4 1 G 4 transition of Pr3 1.004 m .
B. Infrared emission 1.3 m

The infrared emission spectra of a single doped sample with 1 mol % Pr3 and a codoped one with 1 mol % Pr3 : 4 mol % Yb3 are presented in Fig. 2. The band peaks are centered at 1.327 m and have a width of 0.1 m. The inset

FIG. 3. Upconversion spectrum of sample with 1 mol % Pr3 :4 mol % Yb3 obtained at 300 K. The inset shows the variation of the integrated emission band at 0.481 m 20 800 cm 1 as a function of Yb3 concentration.

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Pecoraro et al. TABLE I. Microscopic parameters of energy transfer by the dipoledipole mechanism in Pr3 :Yb3 codoped lead uoroindogalate glasses. Cs a cm6/s 3.45 10 4.46 10 2.10 10
40 41 41

Sensitizeractivator Yb3 Pr3 Pr3 Yb3 Pr3 Pr3

Rc 9.15 4.7 4.2

FIG. 4. Energy level diagram of Pr3 and Yb3 in lead uoroindogallate glasses. The level widths were obtained from absorption spectra.

limit in the Yb3 concentration is 4 mol % and the energy transfer is no longer efcient beyond this value due to Yb3 reabsorption of the incident radiation.
IV. DISCUSSION A. Infrared emission 1.3 m and energy transfer

tral overlap between the sensitizer emission and activator absorption. The emission cross section was obtained using the method proposed by McCumber18 to describe the emission of a two level system taking into consideration the broad absorption and emission bands. This method was generalized by Miniscalco, and Quimby19 to use in glass systems. According to these two studies, the emission cross section can be calculated by means of the absorption cross section, thus
e a

Ze exp E ZL h Zg

/kT ,

Enhancement of the infrared 1.3 m emission of Pr3 by the presence of Yb3 can be understood by looking at the energy level diagram in Fig. 4. The main pumping channel is the Yb3 due to its absorption band 2 F 7/2 2 F 5/2 , which has an integrated absorption cross section nearly 20 times greater than that of the Pr3 ( 1 G 4 3 H 5 ) as seen in Fig. 1. Pr3 is excited by the Yb3 Pr3 energy transfer 2 F 5/2 , 3 H 4 1 G 4 , 2 F 7/2 , which enables it to emit a 1.3 m photon making the transition 1 G 4 3 H 5 . The energy transfer in the Yb3 :Pr3 system is a resonant process that can be treated using the ForsterDexter theory of nonradiative energy transfer between impurities in solids.13 Such a model is based on the electrostatic interactions between the impurities sensitizer and activator and can occur by means of dipoledipole, dipolequadrupole, or quadrupolequadrupole coupling. One requirement for a system to follow the ForsterDexter model is that it must be diluted no cluster formation is accepted .14 Knowing for certain which multipolar coupling is responsible for the nonradiative energy transfer between rare-earth ions is still an open question. Some systematic studies have shown that dipoledipole interaction is the principal mechanism for energy transfer.1517 The rate of energy transfer by dipole dipole interaction can be obtained by the expression Ps
a

where E ZL is the average energy between the emission and absorption peaks, a is the absorption cross section, is the incident photon frequency, and Z e /Z g is the ratio between the excited and ground state partition function, respectively.19 Two microscopic parameters of energy transfer C s a energy transfer constant and R c critical radius of interaction can be dened as follows: Cs
a

Ps

aR

Rc

Cs

a s

1/6

d d

3 c 2Q aQ s 4 3n 2R 6

fs E fa E dE, E2

where n is the refractive index, R is the average distance between the sensitizer and activator, Q a and Q s are the integrated absorption and emission cross sections of the activator and sensitizer, respectively, and f a and f s are the normalized line shape functions of the absorption and emission spectra of the same ions. The integral in Eq. 1 represents the spec-

where s is the sensitizer lifetime in the absence of the activator. The critical radius is the distance where the energy transfer probability is equal to the sensitizer radiative decay rate. It can be noted that a slow sensitizer lifetime leads to a large critical radius which enhances the energy transfer rate. Table I shows the results of the calculation of the microscopic parameters of energy transfer in the Yb3 :Pr3 system. One can see from Table I that the direct energy transfer (Yb3 Pr3 ) is almost 10 times greater than the backtransfer (Pr3 Yb3 ) which leads to an even greater critical radius for the former process. This can be easily understood by looking at the spectral overlap in the two cases. Figures 5 a and 5 b show the normalized line shape functions of the sensitizer emission and activator absorption in the case of direct transfer and backtransfer, respectively. Spectral overlap is obtained with the product of these two spectra. For direct transfer a spectral overlap one order of magnitude greater than that in backtransfer was obtained. The energy transfer constant C YbPr was found to be in very good agreement with the one obtained by Chamarro and Cases for the same ions in uorohafnate glasses.15 Table II presents the average distance R between the ions and the energy transfer probabilities P YbPr and P PrYb of all the codoped samples studied. The average distances were calculated using the formula R 3/(4 N) 1/3 taking into account the fact that the dopants are uniformly distributed. N is the dopant concentration in ions/cm3. It is important to note that the calculated R

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B. Upconversion

FIG. 5. Normalized line shape functions of sensitizer emission and activator absorption, showing the spectral overlap in the case of direct energy transfer a and backtransfer b . It can be seen that spectral overlap is nearly absent in the case of backtransfer. The spectra are normalized so that the area under each curve is equal to 1.

value, for all the samples, is greater than the critical radius for backtransfer. On the other hand, for direct transfer, R is always lower than the critical radius. According to Dexter,13 if one neglects the nonradiative transitions in the sensitizer, the energy transfer efciency can be evaluated by the expression t
s a

The upconversion signal represents a loss mechanism for the infrared emission. As can be seen in Fig. 4, the upconverted emissions are pumped by a two step energy transfer 2 F 5/2 , 2 F 5/2 , 3 H 4 3 P 0 , 2 F 7/2 , 2 F 7/2 . The energy transfer between two Pr3 was discarded due to the low energy transfer constant and the large distance between Pr3 ions (R 10.4 ) which is more than twice the critical radius for this process Table I . Another way to achieve upconversion is the excited state absorption 1 G 4 3 P 0 . This mechanism was discarded in our study since we were not able to observe an upconversion signal in single doped samples.9 All the observed upconverted emissions 3 P 0 3 H 4 at 0.481 m, 3 P 0 3 H 5 at 0.525 m, and 3 P 0 3 H 6 at 0.62 m 5 start from the 3 P 0 level. From 1 mol % Yb3 up to 4 mol % Yb3 , the 1.3 m emission increases by a factor of 2.5 while the upconversion signal increases by a factor of 8. Unfortunately, since we have been unable to compare the absolute intensities of the infrared and upconverted emissions, it is hard to say which one is more efcient. So far, the upconversion is a loss that cannot be removed from the system.
V. CONCLUSION

Ps a Ps

s a s

where P s a is the sensitizeractivator energy transfer probability and s is the sensitizer lifetime without the activator. From this expression it is observed, in some cases, that the lifetime can dene which ion will work as a sensitizer. The sensitizer lifetime ( s ) was measured in single doped samples with low concentration 0.2 mol % of Yb3 or Pr3 in each case assuring an exponential decay curve. For the best sample to emit at 1.3 m (1 mol % Pr3 :4 mol % Yb3 R 6.06 ), we calculated t(s a) considering direct energy transfer Yb3 as the sensitizer and Pr3 as the activator and backtransfer Pr3 as the sensitizer and Yb3 as the activator . For direct transfer, P YbPr 6966 s 1 and Yb 1.7 ms, hence t(YbPr) 92%. In the case of backtransfer, P PrYb 900 s 1 and Pr 0.25 ms, which leads to t(PrYb) 18%. It is worth noting that the multiphonon decay rate in Pr3 is not negligible, but this result can be used as a reference that evidences weak backtransfer efciency and corroborates our previous assumptions.

This study showed that Yb3 :Pr3 codoping of lead uoroindogallate glasses increases the intensity of the 1.3 m Pr3 emission ( 1 G 4 3 H 5 ) up to 40 times through the Yb3 Pr3 energy transfer 2 F 5/2 , 3 H 4 1 G 4 , 2 F 7/2 . It was observed that the rate of energy transfer is nearly 10 times greater from ytterbium to praseodymium ions. The obtained efciency of the energy transfer also showed a tendency for the transfer to occur in the ytterbium to praseodymium direction. The best Pr3 :Yb3 concentration 1:4 ratio was determined by luminescence measurements. It was veried that the upconversion signal is also fed by the Yb3 Pr3 energy transfer. In upconversion and infrared luminescence experiments, the maximum concentration of Yb3 was found to be 4 mol %, suggesting that, at a higher concentration, a large amount of the incident radiation is trapped on the Yb3 .
See, for example, D. W. Hewak et al., Proc. SPIE 2073, 1993 , and references therein. 2 D. M. Baney, G. Rankin, and K. W. Chang, Appl. Phys. Lett. 69, 1662 1996 . 3 H. M. Pask, A. C. Tropper, and D. C. Hanna, Opt. Commun. 134, 139 1997 . 4 M. Yu. Sharonov, Z. I. Zhmurova, E. A. Krivandina, A. A. Bystrova, I. I. Buchinskaya, and B. P. Sobolev, Opt. Commun. 124, 595 1996 . 5 M. Malinowski, Z. Frukacz, M. F. Joubert, and B. Jacquier, J. Lumin. 75, 333 1997 . 6 ` B. Jaquier, C. Linares, R. Mahiou, J. L. Adam, E. Denoue, and J. Lucas, J. Lumin. 60&61, 175 1994 . 7 B. C. Joshi and M. C. Joshi, J. Non-Cryst. Solids 142, 171 1992 . 8 B. C. Joshi, M. C. Joshi, and B. D. Joshi, J. Phys. Chem. Solids 52, 939 1991 . 9 E. Pecoraro, L. A. O. Nunes, R. M. Lebullenger, and A. C. Hernandes unpublished . 10 A. Florez, O. L. Malta, Y. Messaddeq, and M. A. Aegerter, J. Non-Cryst. Solids 213&214, 315 1997 . 11 R. S. Quimby and W. J. Miniscalco, J. Appl. Phys. 75, 613 1994 . 12 A. A. Kornienko, A. A. Kaminskii, and E. B. Dunina, Phys. Status Solidi B 157, 267 1990 .
1

TABLE II. Average distance between the impurities R and energy transfer rates ( P s a ) by the dipoledipole mechanism in Pr3 :Yb3 codoped lead uoroindogalate glasses. Pr3 :Yb3 (mol %) 1:1 1:2 1:4 1:6 R 8.2 7.2 6.1 5.4 P YbPr s1 1094 2476 6966 13914 P PrYb s1 141 320 900 1798

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16 17

Pecoraro et al. M. J. Weber, Phys. Rev. B 4, 2932 1971 . S. Tanabe, T. Kouda, and T. Hanada, Opt. Mater. 12, 35 1999 . 18 D. E. McCumber, Phys. Rev. 136, A954 1964 . 19 W. J. Miniscalco and R. S. Quimby, Opt. Lett. 16, 258 1991 .

D. L. Dexter, J. Chem. Phys. 21, 836 1953 . M. Takahashi, M. Shojiya, Y. Kawamoto, K. Kadono, T. Ohtsuki, and N. Peyghambarian, J. Appl. Phys. 81, 2940 1997 . 15 M. A. Chamarro and R. Cases, J. Non-Cryst. Solids 107, 178 1989 .

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